Fuel additive

ABSTRACT

A fuel additive contains ferrocene and/or ferrocene derivative(s), and lecithin. A fuel additive contains 80 to 99 mass % of ferrocene and/or ferrocene derivative(s), and 1 to 20 mass % of lecithin, and being in the solid state. A fuel additive contains 78 to 99 mass % of ferrocene and/or ferrocene derivative(s), 0.9 to 20 mass % of lecithin and 0.1 to 2 mass % of water, and being in the particle state. A fuel additive containing 2 to 5 mass % of ferrocene and/or ferrocene derivative(s), 5 to 50 mass % of lecithin and mineral oil, and being in the liquid state, wherein the ferrocene and/or ferrocene derivative(s), and the lecithin are dissolved in the mineral oil. The above-mentioned fuel additive is used by being added into a fuel so as to make the concentration of the ferrocene and/or ferrocene derivative(s) and the lecithin in ranges of 1 to 50 ppm, and 0.01 to 500 ppm, respectively.

TECHNICAL FIELD

The present invention relates to a fuel additive containing ferroceneand/or ferrocene derivative(s), and, more particularly, relates to afuel additive containing ferrocene and/or ferrocene derivative(s) towhich functions such as combustion promotion, soot reduction, NOxreduction and the like are enhanced by adding lecithin.

DESCRIPTION OF THE RELATED ART

Conventionally, ferrocene and derivative(s) thereof are used as anadditive for various liquid fuels. For instance, ferrocene,derivative(s) thereof and a improvement combustion method of a liquidhydrocarbon in the presence of a fuel additive composition consisting ofan aromatic solvent, an aliphatic solvent and/or a petroleum solventwhich are liquid organic careers capable of dissolving the ferrocene andderivative(s) thereof are described in JP02-132188A. Moreover, a methodof conditioning of diesel engines is described in U.S. Pat. No.4,389,220 specification. In accordance with the method, a depositcontaining carbon in the combustion chamber is removed, and the fuelconsumption per distance traveled is reduced by about 5%, by adding20-30 ppm of ferrocene to the fuel.

In addition, a method of reducing carbonaceous deposition on the engineand ancillary equipment thereof is proposed in JP Patent 3599337specification. In accordance with the method, 1-100 ppm of ferrocene andderivative(s) thereof, as additives for fuel oil consisting of a heavyresidual oil for an internal combustion, are added to a fuel directly,without blending other additives.

However, ferrocene and ferrocene derivative(s) used for these inventionshave a drawback of very low solubility in an aromatic solvent, analiphatic solvent and a petroleum solvent.

In general, ferrocene is in the solid state. In order to dissolve solidferrocene, in particular, a large quantity of agitation power and longtime, which depend on the size of the solid, are needed. Even if theamount of addition is small, solid ferrocene doesn't dissolve easilyeither. The trouble occurs in the internal combustion engine when solidferrocene isn't dissolved beforehand before it adds to the fuel.Therefore, under the present situation, the solid ferrocene is added toa fuel after it is dissolved in a solvent in a solution tank with anagitator.

DISCLOSURE OF INVENTION

The present invention is made in view of the aforementioned problems ofthe conventional technology and has an object to provide a fuel additivecontaining ferrocene and/or ferrocene derivative(s), which can easilyand stably be dissolved in a fuel.

As a result of repeating assiduous studies for achieving theabove-mentioned object, the present inventors found the object to beaccomplished by using ferrocene and/or ferrocene derivative(s) incombination with lecithin, and have achieved the present invention.

That is, the fuel additive according to the present invention ischaracterized by containing ferrocene and/or ferrocene derivative(s),and lecithin.

The solid fuel additive according to the present invention ischaracterized by containing 80 to 99% by mass of ferrocene and/orferrocene derivative(s), and 1 to 20% by mass of lecithin. Theparticulate fuel additive according to the present invention ischaracterized by containing 78 to 99% by mass of ferrocene and/orferrocene derivative(s), 0.9 to 20% by mass of lecithin and 0.1 to 2% bymass of water.

In addition, the liquid fuel additive according to the present inventionis characterized by containing mineral oil containing ferrocene and/orferrocene derivative(s) and lecithin dissolved therein, and having theferrocene and/or ferrocene derivative(s) content of 2 to 5% by mass andthe lecithin content of 5 to 50% by mass.

Furthermore, the fuel additive according to the present invention ischaracterized by being used by being added into a fuel so as to make theconcentration of the ferrocene and/or ferrocene derivative(s) and thelecithin in ranges of 1 to 50 ppm, and 0.01 to 500 ppm, respectively.

BEST MODE OF CARRYING OUT THE INVENTION

Hereafter, a fuel additive according to this invention will be explainedin detail. In this specification, “%” means “mass percentage” unlessotherwise specified.

As mentioned above, a fuel additive according to this invention is thefuel additive that contains ferrocene and/or ferrocene derivative(s) andlecithin. These fuel additives can be in the solid state, especially inthe particle state, and in the liquid state.

(1) Ferrocene and Ferrocene Derivative(s)

Formally, ferrocene is called bis(cyclopentadienyl) iron, and is alsocalled dicyclopentadienyl iron. Ferrocene derivative(s) used in thisinvention is(are) compound(s) having a structure in which adicyclopentadienyl ring having substituents such as an alkyl group. Asthe ferrocene derivative(s), mention may be made, for example, ofethylferrocene, butylferrocene, acetylferrocene, 2,2-bis-ethylferoseniru propane and the like.

For instance, a manufacturing method of ferrocene and derivative(s)thereof (hereinbelow said to be ferrocenes) is disclosed inspecification of U.S. Pat. Nos. 2,650,756, 2,769,828, 2,834,796,2,898,360, 3,035,968, 3,238,158, 3,437,634, and the like.

In the present invention, ferrocenes may be a solid such as a finepowder, a coarse particle, a pellet and the like, and may be a liquid.The form of ferrocenes can be suitably chosen depending on the form of afuel additive of the present invention. It is explained in detail later.

A fuel additive of the present invention can have a combustion promotioneffect, a soot reduction effect, a NOx reduction effect and the like, bycontaining ferrocenes. In particular, in a diesel engine that is aninternal combustion engine, a cleaning effect of the combustionpromotion that controls the formation of deposit on a valve, a pistonring, and a combustion chamber is observed. Since the deposit reducesengine output and increases attrition of parts by adhering, controllingformation of the deposit achieves stable driving of a diesel engine. Inaddition, several percent reduction of fuel consumption can be realizedby preventing superfluous air at the time of combustion, by thereforming combustion such as combustion promotion, soot reduction, NOxreduction and the like.

(2) Lecithin

Lecithin is an animal and plant phospholipid of which the principalingredients are a glycerophospholipid and a sphingophospholipid. It isobtained by the purification process of various kinds of vegetable oilsuch as soybean oil, rapeseed oil, rice-bran oil, palm oil, sunfloweroil, cocoanut oil, cottonseed oil, corn oil, peanut oil, linseed oil,safflower oil, olive oil and the like. Usually, a vegetable oil isincluded 1 to 50%. Depending on the contained amount of the vegetableoil and the ratio between saturation acid and unsaturated acid in thevegetable oil, lecithin exists in the liquid form or in the solid format normal temperature. Moreover, in recent years, a powder lecithin ismanufactured from a liquid lecithin by carrying out oil extraction andvacuum drying.

In the present invention, lecithin may be a liquid, and may be a solidsuch as a fine powder and the like. The form of lecithin can be suitablychosen depending on the form of a fuel additive of the presentinvention. It is explained in detail later.

(3) A Form of a Fuel Additive

A fuel additive of the present invention can be in the solid state, inthe particle state, and in the liquid state.

(i) Solid Fuel Additive

A solid fuel additive of the present invention preferably contains 80 to99% of ferrocenes and 1 to 20% of lecithin. If the content of thelecithin is less than 1%, the ferrocenes may not dissolve in the fueleasily. If the content of the lecithin is 20%, the ferrocenes solubilityenhancement effect may be obtained completely.

The form of ferrocenes is not especially limited as long as it is solidat normal temperature, mention may be made, for example, of a solid formsuch as a fine powder, a coarse particle, a pellet and the like. Inaddition, lecithin is preferably in the powder form at normaltemperature, more preferably a fine powder of 1 mm or less in particlediameter. It is because the mixture with Ferrocenes may be made moreuniform.

(ii) Particulate Fuel Additive

A particulate fuel additive of the present invention is one aspect ofthe above-mentioned solid fuel additive, and is granulated from finepowder ferrocene compound into the shape of a coarse particle. As forthe particle diameter, it is preferable to be 0.5 mm to 15 mm, morepreferably 1 mm to 10 mm. When the particle diameter is less than 0.5mm, the handling workability may be inferior due to powder dust. Whenthe particle diameter is more than 15 mm, the solubility may decreasedue to decreased deflocculability.

A particulate fuel additive preferably contains 78 to 99% of ferrocenes,0.9 to 20% of lecithin and 0.1 to 2% of water. If the content of thelecithin is less than 0.9%, the ferrocenes may not dissolve in the fueleasily. If the content of the lecithin is 20%, the ferrocenes solubilityenhancement effect may be obtained completely.

Ferrocenes are preferably in the powder form at normal temperature, morepreferably a fine powder of 2 mm or less in particle diameter. Inaddition, lecithin is also preferably in the powder form at normaltemperature, more preferably a fine powder of 1 mm or less in particlediameter. It is for the convenience of granulation process.

A powder lecithin used in this invention has high hygroscopicity, andobtains suitable tackiness for a granulation by mixed with small amountof water. However, when the content of the water is less than 0.1%, thesufficient tackiness may not be obtained, and when the content of thewater is more than 2%, the above-mentioned powder ferrocenes and theabove-mentioned powder lecithin may be agglomerated due to high watercontent.

(iii) Liquid Fuel Additive

A liquid fuel additive of the present invention contains mineral oilcontaining ferrocene and/or ferrocene derivative(s) and lecithindissolved therein, and preferably the content of the ferrocene and/orferrocene derivative(s) is 2 to 5% and the content of the lecithin is 5to 50%. If the content of the lecithin is less than 5%, the ferrocenesmay not dissolve in the mineral oil easily. If the content of thelecithin is 50%, the effect of enhancing solubility of ferrocenes inmineral oil may be obtained completely.

The ferrocenes may be a solid such as a fine powder, a coarse particle,a pellet and the like, or may be a liquid, preferably a liquid or a finepowder from the viewpoint of shape that dissolves easily in mineral oil.And similarly, the lecithin may also be a liquid, or a solid such as afine powder and the like, preferably a liquid or a fine powder, becauseof the shape thereof that dissolves easily in mineral oil.

As used herein, the term “mineral oil” includes hydrocarbon fuel oil,gas oil, kerosene and the like. For example, for use in grade C heavyoil used as a fuel of large-scale diesel engines for marine vessels,grade A heavy oil, grade B heavy oil, gas oil, kerosene and the like canbe preferably used, and grade A heavy oil can be more preferably used.

(4) Action and Effect of Lecithin

Lecithin in the present invention mainly provides the effect as follows.

i) Enhancement of solubility in fuel of ferrocenesii) Dispersing action of sludge in fuel oiliii) Binder action at the time of granulation to prepare a particulatefuel additiveiv) Deflocculation action in a particulate fuel additivev) Enhancement of solubility in mineral oil of ferrocenes, in a liquidfuel additive

Each above-mentioned effect is described below.

i) Enhancement of Solubility in Fuel of Ferrocenes

Ferrocenes have a drawback of low solubility in various fuels, asmentioned above. As used herein, the term “fuel” includes fuels used asa fuel for diesel engines, oil incinerators, boiler devices and thelike, such as grade A heavy oil, light oil such as kerosene, gas oil andthe like, heavy oil, heavy residue oil, lubricating oil, waste oil andmixed oil thereof, and also fuel emulsion thereof, and solid fuel suchas coal and the like, but are not limited thereto, as long as the fuelis not in gaseous form.

For instance, in case of single ferrocene, a solubility in petroleumsolvents such as aromatic solvent other than benzene, toluene andxylene, aliphatic solvent and the like is very low. Thus, in such asolvent as above mentioned, single ferrocene is soluble only up to 3% inconcentration at 20 degree C. In addition, ferrocenes concentration insolvent for prolonged stability is preferably 2.5% or less. The samegoes for when ferrocenes is dissolved in fuel such as heavy oil and thelike. However, by adding the prescribed amount of lecithin, it ispossible for ferrocenes to be dissolved up to 5% in concentration, andthe stability of the solution is good in a broad temperature region.

The relation between the additive amount of lecithin and the maximumsolubility of ferrocenes in grade A heavy oil is shown in Table 1.

TABLE 1 Lecithin Grade A Heavy Oil Maxmum Solubility of Ferrocenes (mass%) (mass %) (mass %) — 97.7 2.3  5.0 90.1 4.1 10.0 85.4 4.6 20.0 74.95.1 30.0 65.3 4.7 40.0 55.6 4.4 50.0 49.6 4.1 The results of stabilitytest for 1 week at room temperature Lecithin = liquid lecithin Grade AHeavy Oil (sulfer content = 0.09%, viscosity = 2.8 cst (at 50° C.))

Thus, since ferrocenes is easily dissolved in a fuel of variouscombustion facilities or in a fuel additive itself by adding lecithinthat has a solubility enhancement effect, and a stable solution can beobtained, it becomes possible to spray ferrocenes in the uniformparticle form on a combustion engine. As a result, the action and effectof ferrocenes can be exerted more than enough.

Lecithin has an oleophilic portion and a hydrophilic portion, and isknown to act as a surfactant agent. However, in the present invention,it is considered that lecithin enhances the solubility due to the actionof an oleophilic portion. That is, it is considered as follows. Whenferrocenes and lecithin are dissolved in a fuel, one part of oleophilicportions of the lecithin promptly adsorb to the surface of theferrocenes, and another oleophilic portions of the lecithin enhancelipophilic property on the surface of the ferrocenes, therefore,lecithin contribute to the solubility enhancement of ferrocenes in afuel.

These actions are not seen in any other surfactant agents such asnonionic surfactant and the like, and are peculiar to lecithin.

ii) Dispersing Action of Sludge in Fuel Oil.

This action differs from the above mentioned solubility enhancementaction of ferrocene. Lecithin itself acts as a fuel additive, andcontributes to long-term stable operation of the combustion facilityincluding a diesel engine.

Sludge is an insoluble matter, which exists in a fuel oil, especially ina heavy oil, and causes clogging of a strainer and incomplete combustionsince it is easy to precipitate. A generation of the sludge arises fromchange into a hydrocarbon polymer having few hydrogen atoms byoxidation, polymerization and condensation of hydrocarbon that remainsin a oil residue in a tank, because of heat-treatment, catalyticcracking, pyrolysis and the like during a purification process of crudeoil.

The above-mentioned change takes place in order of hydrocarbon,malthene, asphaltene, carbine, carboid and carbon. These polymersinitially exist in a heavy oil as a macromolecular colloid. It isconsidered that the colloid has a hydrocarbon such as carbine, carboidand the like as a core with an extremely high C/H ratio, surrounded bysome asphaltenes, and covered sequentially with hydrocarbon polymer witha low C/H ratio.

An asphaltic substance that exists in a heavy oil as such a colloidalparticle will not be precipitated and cause the problem of clogging of astrainer, incomplete combustion and the like, as long as it is floatingdispersedly as stable colloid. However, this colloidal particle haspolarity and adsorptivity property. Therefore, if equilibrium conditionis disrupted by heating, adding an oil of a different kind, prolongedstorage and the like, the colloidal particles agglutinate together oneafter another, and get into an aggregate of big particles (micellecolloid), and form sludge by precipitating.

Specifically, when a light component is added to a heavy oil containingthe above-mentioned colloidal particle, hydrocarbon polymers andmalthene of the colloid surface layer is dissolved. However, sinceasphaltene, carboid and the like are unsaturation and have polarity, thecolloidal particles agglutinate each other, the huge asphalteneparticles are separated, and sludge is formed. In addition, when heat isapplied, a colloid surface layer is dissolved and also particle motionis increased because viscosity is reduced by a rise in heat. And sludgeis formed by binding and association, since opportunities for collisionof the asphaltenes are augmented.

Lecithin infiltrates and absorbs to binding portion and/or associationof sludge such as carbon, asphaltene and the like, and has a mincingaction of sludge by dispersion force by acting as a surfactant agent.Lecithin also has the effect of preventing separation and precipitationof sludge, by preventing mixing of different-type fuels, association ofthe colloidal particles by heating and the like, by this action.

iii) Binder Action at the Time of Granulation to Prepare a ParticulateFuel Additive.

As mentioned above, when a particulate fuel additive is granulated,lecithin obtains suitable tackiness for a granulation by mixed withsmall amount of water, and bears a role of a binder.

iv) Deflocculation Action in a Particulate Fuel Additive.

Lecithin contained in particulate fuel additives has deflocculationaction to make particles easy to crush when the additive is fed into afuel. In addition, the crushed additive comes to dissolve very easily bysolubility enhancement effect of lecithin.

v) Enhancement of Solubility in Mineral Oil of Ferrocenes, in a LiquidFuel Additive

Ferrocenes have a very low solubility in mineral oil, and are solubleonly up to about 2.5% in concentration.

However, by adding the prescribed amount of lecithin, it is possible forferrocenes to be dissolved up to 5% in concentration, and the stabilityof the solution is good in a broad temperature region.

(5) Concentration in a Fuel of Ferrocenes and Lecithin.

It is preferred that the fuel additive according to the presentinvention for various fuels used for diesel engines, oil incinerators,boiler devices and the like, which are used in a marine vessels, powergenerating facilities and the like, is added into the fuels so as tomake the concentration of ferrocene and/or ferrocene derivative(s) andlecithin in ranges of 1 to 50 ppm, and 0.01 to 500 ppm, respectively.

More specifically, as for usual concentration of ferrocenes, it ispreferred that the fuel additive is added sequentially into the fuels inorder that the fuels in oil incinerators and boiler devices haveferrocene and/or ferrocene derivative(s) concentration of 1-10 ppm andthe fuels in diesel engine have ferrocene and/or ferrocene derivative(s)concentration of 10-50 ppm.

However, in order to greatly improve objective combustion promotion,soot reduction, NOx reduction and the like, several fold to dozens ofthe continuous additive amount can be temporarily added while a shorttime, based on the condition of a combustion engine.

The above-mentioned lecithin has advantageous concentration to dissolveeasily and stably ferrocenes in a fuel oil and in fuel additive itself,and to disperse sludge further, in a heavy fuel oil especially.

In this manner, by dissolving ferrocenes easily and stably withdesirable concentration of lecithin, the action and effect of ferrocenescan be exerted more than enough and it can contribute to long-termstabile operation of combustion facilities.

EXAMPLES

Hereinafter, this invention is further explained in detail on basis ofexamples and comparative example, but this invention is not limited tothese examples.

Evaluation of various characteristics was carried out in the followingway.

Evaluation of a Solubility Test of Ferrocenes Solid Fuel AdditiveExample 1-4 and Comparative Example 1

Ferrocene was added to 200 g of grade A heavy oil (sulfur content=0.09%,viscosity=2.8 cst (50 degree C.)) as a fuel oil, stirring at 20 degreeC. and 60 rpm, and the rate of solution until ferrocene concentrationreaches 3% was evaluated by measuring the number of seconds. Then,ferrocene was added further in order to produce the stable solution ofmaximum concentration, and stability after still standing for one weekat room temperature was evaluated. The results are shown in Table 2.

Liquid Fuel Additive Example 5-7 and Comparative Example 2

While stirring at 20 degree C. and 60 rpm, the fuel additives wereprepared by compositions shown in Table 3, and the rate of solutionuntil ferrocene is completely dissolved in grade A heavy oil wasevaluated by measuring the number of seconds. Stability of the obtainedsolution after still standing for one week at room temperature wasevaluated. The test was done on a 200 g scale. The results are shown inTable 3.

TABLE 2 Example Comparative Example 1 2 3 4 1 additive Ferrocene 80 9894.5 79 100 composition Lecithin 20 2 5 20 — [%] (Solid) Water — — 0.5 1— Total 100 100 100 100 100 solubility rate 180 370 290 175 660dissolved concentration 4.8 3.5 4.1 4.9 3.0 stability test very goodgood very good good no good Lecithin (Solid) means a powdered lecithinin the solid state, lecithin (liquid) means a lecithin in the liquidstate. Stability test: “very good” mesns complete dissolution, “good”mesns almost dissolution, “passed” mesns a little insoluble matter wasobserved, “no good” mesns too much insoluble matter was observed.

TABLE 3 Example Comparative Example 5 6 7 2 additive Ferrocene 3.5 5.04.0 2.5 composition Lecithin 5 20 50 — [%] (Liquid) Water — — — — GradeA Heavy Oil 92 75 46 97.5 Total 100 100 100 100 solubility rate 110 190120 580 dissolved concentration 3.5 5.0 4.0 2.5 stability test very goodgood good passed Lecithin (Solid) means a powdered lecithin in the solidstate, lecithin (liquid) means a lecithin in the liquid state. Stabilitytest: “very good” mesns complete dissolution, “good” mesns almostdissolution, “passed” mesns a little insoluble matter was observed, “nogood” mesns too much insoluble matter was observed.

Results

The rate of solution of solid fuel additives of the present invention(Example 1-4) until ferrocene concentration reaches 3% is very fast ascompared with comparative example 1. The concentration of a stablesolution of comparative example 1 is 3% but with many insoluble matters,while the concentration of a stable solution of example 1-4 is allowedto be 3.5 to 5.0%. In addition, the evaluations of stability afterstoring for one week of Example 1-4 are “very good” or “good”. Thus, itwas confirmed that a solid fuel additive of this invention was veryexcellent in all aspects of solution rate of ferrocene, dissolvedconcentration and stability evaluation.

At the time of preparation of fuel additive, the rate of solution ofliquid fuel additives of the present invention (Example 5-7) untilferrocene is completely dissolved in grade A heavy oil is very fast ascompared with comparative example 2. In addition, the evaluations ofstability after storing for one week are “very good” or “good”. Thus, itwas confirmed that a liquid fuel additive of this invention was veryexcellent in all aspects of solution rate of ferrocene, dissolvedconcentration and stability evaluation.

[Dispersing Effect of Sludge]

Sludge dispersion tests of examples and comparative examples describedin Table 2 and Table 3 were done. The tests were applied to The JapaneseShipowners' Association method.

Operating Procedure

(1) Into a test tube, 0.1 g of grade C heavy oil was taken, and 20 ml ofnormal heptane was added to this test tube. In addition, 0.02 ml(1/1000) of fuel additive of Examples 1-7 or comparative examples 1-2was added.(2) The test tube was sealed and strongly shaken 20 times or more untilthoroughly mixed.(3) The test tube was settled at room temperature and the dispersionstate of every elapsed time was evaluated by the following standard.

Evaluation Standard

A . . . . Complete dispersion and no precipitationB . . . . Dispersion and precipitation

It is referred to as B1, B2 and B3 in order of increasing amount ofprecipitation.

C . . . No dispersion and precipitated almostThe results are shown in Table 4.

TABLE 4 soon after 8 hours 24 hours 48 hours mixed after after afterExample 1 A A A A~B1 2 A A~B1 B1~B2 B2 3 A A A~B1 B1 4 A A A A~B1 5 A AA~B1 B1 6 A A A A~B1 7 A A A A~B1 Comparative 1 A C C C Example 2 A C CC Additive-free A C C C Properties of Grade C heavy oil applied to theevaluation Density (15° C.): 0.955 Viscosity (50° C.): 358 cst Sulfercontent (%): 3.07 Carbon Residue content (%): 11.6 Asphaltene (%): 6.94

Results

A solid fuel additive of this invention (Examples 1-4) and a liquid fueladditive of this invention (Examples 5-7) have a very excellent effectof sludge dispersion as compared with comparative example 1, 2 andadditive-free. Comparative examples 1 and 2, which do not containlecithin, had no effect at all and were the same as additive-free gradeC heavy oil. An effect of lecithin was the result of being proportionalto an additive amount in general.

[Measurement of Combustion Rate]

When 10 mg of fuel oil (grade C heavy oil, the same oil as used foreffect evaluation of the above-mentioned sludge dispersion), to whichwas added liquid fuel additive (examples 5-7) of this invention orliquid fuel additive of the comparative example 2, was heated to 500degree C. with a rate of temperature rise of 100 degree C./min.) andcombusted (m1 represents mass of an end point of carbon residuegeneration), and kept at 500 degree C. by using Differential thermalanalysis system TG/DTA6300 (made by Seiko Instruments Inc.), TG(thermogravimetric analysis) carbon residue combustion rate constant wascomputed from the mass reduction curve of generated carbon residue (m2represents mass of 95% burned point). The quantity of airflow was 100ml/min. Following formula (I) was used for the calculating method. *1,*2

TG carbon residue combustion rate constant=AxTxIn(m1/m2)/tau  (I)

A: constantT: temperaturem1: mass of an end point of carbon residue generationm2: mass of 95% burned pointtau: (m2-m1) time*1 Shibayama et al., the Japan Society of Mechanical Engineers collectedpapers, 34 (260), 769 (1968)*2 Hou et al., the Japan Society of Mechanical Engineers collectedpapers, 54 (507) 3301 (1988)The test results are shown in Table 5.

TABLE 5 TG carbon residue combustion relative rate additive amount rateconstant constant Example 5  500 ppm 16.21 1.030 6  500 ppm 16.26 1.0337  500 ppm 16.51 1.048 5 1000 ppm 19.20 1.220 6 1000 ppm 19.76 1.255 71000 ppm 19.55 1.242 Comparative 2 1000 ppm 15.74 1 Example 2 2000 ppm18.27 1.161 relative rate constant = relative constant that assumed“1,000 ppm of comparison example 2” to be 1

Results

As compared with 1000 ppm addition of comparative example 2, as for 1000ppm addition of liquid fuel additive of this invention (examples 5-7),high TG carbon residue combustion rate constant (relative velocityconstant) was obtained. Since the content of ferrocene was high level,it was a foregone conclusion. However, also as for 500 ppm addition ofExamples 5-7, TG carbon residue combustion rate constant (relativevelocity constant) was higher than that of 1000 ppm addition of thecomparative example 2. In addition, as for 1000 ppm addition of Examples5-7, TG carbon residue combustion rate constant (relative velocityconstant) was higher than that of 2000 ppm addition of the comparativeexample 2.

This can be imagined to be a synergistic effect between solubilityenhancement and sludge dispersion of lecithin on ferrocene. As for thecomparative example 2 that does not contain lecithin, it is consideredthat solubility is insufficient also in fuel oil because ferrocene isunstable in liquid additive. Additionally, it is considered that theeffect was inferior to example 5-7 since there is not a sludgedecentralization effect either when a relative content of ferrocenes wasthe same.

[A System Examination by a Diesel Engine]

The system examination of a cargo boat with a diesel engine of thefollowing specification was done, by using solid fuel additive of thisinvention (example 3) and solid fuel additive of comparative example 1.

The system examination was done, namely, in a solution tank with anagitator, 9.0 Kg of solid fuel additive was dissolved in 360 liters ofgrade A heavy oil, and was added of 1/1000 into the fuel (grade C heavyoil) line from this solution tank with injection pump. (The additiveamount of fuel additive was 25 ppm.)

A solid fuel additive of Example 3 or comparative example 1 was added bythe above-mentioned method over four months alternately per one month(30 days) (one month×2 times for each solid fuel additive). Then, a fuelconsumption and condition of dirt of a heat exchanger by visualobservation was compared. Next, water-wash was performed and dirtremoval performance was compared.

Specification of a Cargo Boat

Gross tonnage: 160,000 t

Deadweight tonnage: 300,500 t

Continuous maximum power: 21,300 kW×74 rpm

Number of cylinders: ten pieces

Revolutions of a turbosupercharger: 10,000 rpm

Fuel consumption: 90,000 L/day (additive-free)

Test results are shown in Table 6.

TABLE 6 Example 3 Comparative Example 1 fuel consumption first 2,597 KL2,660 KL second 2,566 KL 2,647 KL dirt of a heat exchange mechanismfirst Very little deposit adhered to A deposit almost adhered to the thesurface. entire surface thinly. second same as above same as aboveremovability of dirt of a heat first removed by easy rinsing with A lotof time of washing with exchange mechanism by flushing water water wasneeded until removed. with water second same as above same as aboveGeneral Properties of a fuel oil (Grade C heavy oil) Density (15° C.):0.984 Viscosity (50° C.): 401 cst Sulfer content (%): 3.61 CarbonResidue content (%): 13.4 Asphaltene (%): 8.98

Since it was an examination with real ship, fuel consumption wasinfluenced by a wind, flow of tide, difference of output and the like,however, since the results of two examinations became comparable, theevaluation can be judged to be credible.

As for a solid fuel additive of this invention (Example 3), although theadditive amount of ferrocene itself was more slightly fewer thancomparative example 1, the results showed that the fuel consumption wasalso less. This means that the combustion efficiency was improvedsynthetically and synergistically, because lecithin enhances solubilityof ferrocene and a stabilized fuel atomization was realized bydispersion effect of sludge of lecithin itself. In addition, since thecombustion promotion effect was enhanced, dirt of a heat exchanger wascleaner than comparative example 1. And an advantage such as the dirtwas removed by easy rinsing with water was observed.

In the same way, when fuel additive of Example 3 was dissolved in asolution tank, it was dissolved by prompt breakup and dispersionthoroughly in about 10 minutes just after the addition and it wasconfirmed that neither a precipitation nor a float at all were seen inthe solution tank during the procedure. On the other hand, as for a fueladditive of comparative example 1, a float was partially seen in about30 minutes after stirring and, as for the inside of a solution tank, aprecipitate and a float of ferrocene insoluble were seen also during theprocedure.

INDUSTRIAL APPLICABILITY

According to this invention, by using ferrocene and/or ferrocenederivative(s) together with lecithin, the fuel additive in which theferrocene and/or the ferrocene derivative(s) contained can be dissolvedeasily and stably can be provided.

1. A fuel additive containing ferrocene and/or ferrocene derivative(s),and lecithin.
 2. The fuel additive according to claim 1, containing 80to 99 mass % of said ferrocene and/or ferrocene derivative(s), and 1 to20 mass % of said lecithin, and being in the solid state.
 3. The fueladditive according to claim 1, containing 78 to 99 mass % of saidferrocene and/or ferrocene derivative(s), 0.9 to 20 mass % of saidlecithin and 0.1 to 2 mass % of water, and being in the particle state.4. The fuel additive according to claim 1, containing 2 to 5 mass % ofsaid ferrocene and/or ferrocene derivative(s), 5 to 50 mass % of saidlecithin and mineral oil, and being in the liquid state, wherein theferrocene and/or ferrocene derivative(s), and the lecithin are dissolvedin said mineral oil.
 5. The fuel additive according to claim 1, whereinsaid additive is used by being added into a fuel so as to make theconcentration of said ferrocene and/or ferrocene derivative(s) and saidlecithin in ranges of 1 to 50 ppm, and 0.01 to 500 ppm, respectively. 6.The fuel additive according to claim 2, wherein said additive is used bybeing added into a fuel so as to make the concentration of saidferrocene and/or ferrocene derivative(s) and said lecithin in ranges of1 to 50 ppm, and 0.01 to 500 ppm, respectively.
 7. The fuel additiveaccording to claim 3, wherein said additive is used by being added intoa fuel so as to make the concentration of said ferrocene and/orferrocene derivative(s) and said lecithin in ranges of 1 to 50 ppm, and0.01 to 500 ppm, respectively.
 8. The fuel additive according to claim4, wherein said additive is used by being added into a fuel so as tomake the concentration of said ferrocene and/or ferrocene derivative(s)and said lecithin in ranges of 1 to 50 ppm, and 0.01 to 500 ppm,respectively.